Herbicidal α-(5-aryloxy-naphthalen-1-yl-oxy)-propionic acid derivatives

ABSTRACT

Herbicidal α-(5-aryloxy-naphthalen-1-yl-oxy)-propionic acid derivatives of the formula ##STR1## in which R 1  stands for hydrogen, halogen, cyano or trifluoromethyl, 
     R 2  stands for hydrogen or halogen, 
     R 3  stands for halogen, cyano, trifluoromethyl or trifluoromethoxy, 
     R 4  stands for hydrogen or halogen, 
     R 5  stands for hydrogen or halogen and 
     Z stands for halogen, hydroxyl, amino, alkylamino, alkenylamino, alkinylamino, arylamino, aralkylamino, alkoxycarbonylalkylamino, cyanamino, dialkylamino, dialkenylamino, alkylsulphonylamino, arylsulphonylamino, hydroxylamino, alkoxyamino, hydrazino, alkylsulphonylhydrazino, arylsulphonylhydrazino, alkylthio, arylthio, aralkylthio, alkoxycarbonylalkylthio or for the --O--R 6  group, wherein R 6  can be various organic radicals. 
     The starting material naphthol of the formula ##STR2## is also new.

The invention relates to new α-(5-aryloxy-naphthalen-1-yl-oxy)-propionicacid derivatives, processes and new intermediates for their preparationand their use as herbicides.

It has already been disclosed that certain7-aryloxy-naphthalen-2-yl-oxy-carboxylic acid derivatives, such as, forexample, ethylα-(7-(2-chloro-4-trifluoromethylphenoxy)-naphthalen-2-yl-oxy)-propionate,are herbicidally active (compare EP-A 179,015). The action of theseknown compounds against weeds and their tolerability by cultivatedplants are, however, not always satisfactory.

New α-(5-aryloxy-naphthalen-1-yl-oxy)-propionic acid derivatives of thegeneral formula (I) ##STR3## in which R¹ stands for hydrogen, halogen,cyano or trifluoromethyl,

R² stands for hydrogen or halogen,

R³ stands for halogen, cyano, trifluoromethyl or trifluoromethoxy,

R⁴ stands for hydrogen or halogen,

R⁵ stands for hydrogen or halogen and

Z stands for halogen, hydroxyl, amino, alkylamino, alkenylamino,alkinylamino, arylamino, aralkylamino, alkoxycarbonylalkylamino,cyanamino, dialkylamino, dialkenylamino, alkylsulphonylamino,arylsulphonylamino, hydroxylamino, alkoxyamino, hydrazino,alkylsulphonylhydrazino, arylsulphonylhydrazino, alkylthio, arylthio,aralkylthio, alkoxycarbonylalkylthio or for the --O--R⁶ group,

wherein

R⁶ stands for an optionally halogen-substituted radical from the seriescomprising alkyl, alkenyl, alkinyl, alkoxyalkyl, alkylthioalkyl,alkylsulphinylalkyl, alkylsulphonylalkyl, aryloxyalkyl,trialkylsilylalkyl, arylthioalkyl, aralkoxyalkyl, aralkylthioalkyl,alkoxycarbonylalkyl, alkylaminocarbonylalkyl, aralkyl, azolylalkyl,alkylideneamino or for an ammonium equivalent, an alkylammoniumequivalent, an alkali metal equivalent or an alkaline earth metalequivalent or for the group ##STR4## wherein R⁷ stands for hydrogen,alkyl, aryl, furyl, thienyl or pyridyl,

R⁸ stands for alkyl or alkoxy,

R⁹ stands for alkoxy and

Q stands for oxygen or sulphur, or

R⁶ stands for the --(CH₂)_(n) --R¹⁰ group,

wherein

R¹⁰ stands for a heterocyclic radical from the series comprising furyl,tetrahydrofuryl, oxotetrahydrofuryl, thienyl, tetrahydrothienyl,perhydropyranyl, oxazolyl, thiazolyl, thiadiazolyl, dioxolanyl,perhydropyrrolyl, oxoperhydropyrrolyl, pyridinyl or pyrimidinyl, each ofwhich is optionally substituted by halogen and/or alkyl, and n standsfor the numbers 0, 1 or 2,

have now been found.

The compounds of the formula (I) contain at least one asymmetricallysubstituted carbon atom and can therefore exist in differentenantiomeric forms. The invention relates both to the possibleindividual isomers and to the mixtures of these isomers.

It has further been found that the newα-(5-aryloxynaphthalen-1-yl-oxy)-propionic acid derivatives of theformula (I) are obtained when

(a) 5-aryloxy-1-naphthols of the general formula (II) ##STR5## in whichR¹, R², R³, R⁴ and R⁵ have the abovementioned meanings,

are reacted with propionic acid derivatives of the general formula (III)##STR6## in which Z has the abovementioned meaning and

Y stands for a nucleophilic leaving group, if appropriate in thepresence of an acid acceptor and if appropriate in the presence of adiluent, or

(b) halogeno-benzene derivatives of the general formula (IV) ##STR7## inwhich R¹, R², R³, R⁴ and R⁵ have the abovementioned meanings and

X stands for halogen,

are reacted with α-(5-hydroxy-naphthalen-1-yl-oxy)-propionic acidderivatives of the general formula (V) ##STR8## in which Z has theabovementioned meaning,

if appropriate in the presence of an acid acceptor and if appropriate inthe presence of a diluent, or

(c) for the case in which Z stands for hydroxyl and the radicals R¹ toR⁵ have the abovementioned meanings, when compounds of the generalformula (I) in which Z stands for methoxy or ethoxy, and the radicals R¹to R⁵ have the abovementioned meanings, are reacted with an alkali metalhydroxide in the presence of water and if appropriate in the presence ofan organic solvent and are then acidified--if appropriate afterconcentration--using a mineral acid, or

(d) for the case in which Z stands for halogen and the radicals R¹ to R⁵have the abovementioned meanings, when compounds of the general formula(I) in which Z stands for hydroxyl and the radicals R¹ to R⁵ have theabove-mentioned meanings, are reacted with a halogenating agent, ifappropriate in the presence of a catalyst and if appropriate in thepresence of a diluent, or

(e) for the case in which Z, with the exception of halogen, has theabovementioned meaning and the radicals R¹ to R⁵ have the abovementionedmeanings, when compounds of the general formula (I) in which Z standsfor halogen and the radicals R¹ to R⁵ have the abovementioned meanings,are reacted with compounds of the general formula (VI)

    H--Z                                                       (VI)

in which

Z, with the exception of halogen, has the abovementioned meaning,

if appropriate in the presence of an acid acceptor and if appropriate inthe presence of a diluent, or

(f) for the case in which Z stands for the --O--R⁶ group, wherein R⁶,with the exception of ammonium, alkylammonium, alkali metal and alkalineearth metal, has the abovementioned meaning and the radicals R¹ to R⁵have the abovementioned meanings, when compounds of the general formula(I) in which Z stands for hydroxyl and the radicals R¹ to R⁵ have theabovementioned meanings, are reacted with compounds of the generalformula (VII)

    X.sup.1 --R.sup.6                                          (VII)

in which

R⁶, with the exception of ammonium, alkylammonium, alkali metal andalkaline earth metal, has the abovementioned meanings and

X¹ stands for halogen,

if appropriate in the presence of an acid acceptor and if appropriate inthe presence of a diluent.

Finally, it has been found that the newα-(5-aryloxy)-naphthalen-1-yl-oxy)-propionic acid derivatives of thegeneral formula (I) exhibit strong herbicidal properties.

Surprisingly, the α-(5-aryloxy-naphthalen-1-yl-oxy)-propionic acidderivatives of the formula (I) according to the invention show, togetherwith good tolerability in important cultivated plants, substantiallystronger action against certain problem weeds, such as in particularmillet species than ethylα-(7-(2-chloro-4-trifluoromethylphenoxy)-naphthalen-2-yl-oxy)-propionate,which is a structurally similar previously known active compound with anequivalent type of action.

The invention preferably relates to compounds of the formula (I) inwhich

R¹ stands for hydrogen, fluorine, chlorine, bromine, cyano ortrifluoromethyl,

R² stands for hydrogen, fluorine or chlorine,

R³ stands for fluorine, chlorine, bromine, cyano, trifluoromethyl ortrifluoromethoxy,

R⁴ stands for hydrogen, fluorine or chlorine,

R⁵ stands for hydrogen, fluorine, chlorine or bromine and

Z stands for chlorine, hydroxyl, amino, C₁ -C₆ -alkylamino, C₃ -C₄-alkenylamino, C₃ -C₄ -alkinylamino, phenylamino, benzylamino, C₁ -C₄-alkoxycarbonyl-C₁ -C₂ -alkylamino, cyanamino, di-(C₁ -C₄ -alkyl)-amino,di-(C₃ -C₄ -alkenyl)-amino, C₁ -C₄ -alkylsulphonylamino,phenylsulphonylamino, tolylsulphonylamino, hydroxylamino, C₁ -C₆-alkoxyamino, hydrazino, C₁ -C₄ -alkylsulphonylhydrazino,phenylsulphonylhydrazino, tolylsulphonylhydrazino, C₁ -C₄ -alkylthio,phenylthio, benzylthio, C₁ -C₄ -alkoxy-carbonyl-C₁ -C₂ -alkylthio or forthe --O--R⁶ group,

wherein

R⁶ stands for a radical from the series comprising C₁ -C₆ -alkyl, C₃ -C₄-alkenyl, C₃ -C₄ -alkinyl, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, C₁ -C₄-alkylthio-C₁ -C₄ -alkyl, C₁ -C₄ -alkylsulphinyl-C₁ -C₄ alkyl, C₁ -C₄-alkylsulphonyl-C₁ -C₄ -alkyl, phenoxy-C₁ -C₃ -alkyl,trimethylsilylmethyl, phenylthio-C₁ -C₃ -alkyl, benzyloxy-C₁ -C₃ -alkyl,benzylthio-C₁ -C₃ -alkyl, C₁ -C₄ -alkoxy-carbonyl-C₁ -C₂ -alkyl, C₁ -C₄-alkylamino-carbonyl-C₁ -C₂ -alkyl, benzyl, pyrazolyl-C₁ -C₄ -alkyl orC₂ -C₄ -alkylideneamino, each of which is optionally substituted byfluorine and/or chlorine, or for an ammonium equivalent, a C₁ -C₄-alkylammonium equivalent, or a sodium equivalent potassium equivalentor calcium equivalent, or for the group ##STR9## wherein R⁷ stands forhydrogen, C₁ -C₄ -alkyl, phenyl, furyl, thienyl or pyridyl,

R⁸ stands for C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy,

R⁹ stands for C₁ -C₄ -alkoxy and

Q stands for oxygen or sulphur,

or

R⁶ stands for the --(CH₂)_(n) --R¹⁰ group,

wherein

n stands for the numbers 0, 1 or 2 and

R¹⁰ stands for a heterocyclic radical from the series comprising furyl,tetrahydrofuryl, oxotetrahydrofuryl, thienyl, tetrahydrothienyl,perhydropyranyl, oxazolyl, thiazolyl, thiadiazolyl, dioxolanyl,perhydropyrrolyl, oxoperhydropyrrolyl, pyridinyl or pyrimidinyl, each ofwhich is optionally substituted by fluorine, chlorine, bromine and/or C₁-C₄ -alkyl.

The invention relates in particular to compounds of the formula (I) inwhich

R¹ stands for hydrogen, cyano, fluorine or chlorine,

R² stands for hydrogen, fluorine or chlorine,

R³ stands for trifluoromethyl,

R⁴ stands for hydrogen, fluorine or chlorine,

R⁵ stands for hydrogen, fluorine or chlorine and

Z stands for chlorine, hydroxyl, amino, C₁ -C₄ -alkylamino, phenylamino,C₁ -C₄ -alkoxy-carbonyl-C₁ -C₂ -alkylamino, di-(C₁ -C₃ -alkyl)-amino, C₁-C₄ -alkylsulphonylamino, phenylsulphonylamino, hydroxylamino,cyanamino, C₁ -C₄ -alkoxyamino, hydrazino, C₁ -C₄-alkylsulphonylhydrazino, phenylsulphonylhydrazino, C₁ -C₄ -alkylthio orC₁ -C₄ -alkoxy-carbonyl-C₁ -C₂ -alkylthio or for the --O--R⁶ group,

wherein

R⁶ stands for C₁ -C₄ -alkyl, C₁ -C₂ -alkoxy-C₁ -C₂ -alkyl, C₁ -C₂-alkylthio-C₁ -C₂ -alkyl, C₁ -C₂ -alkylsulphinyl-C₁ -C₂ -alkyl, C₁ -C₂-alkylsulphonyl-C₁ -C₂ -alkyl, benzyloxy-C₁ -C₃ -alkyl, benzylthio-C₁-C₃ -alkyl, C₁ -C₄ -alkoxycarbonyl-C₁ -C₂ -alkyl, C₁ -C₄-alkylaminocarbonyl-C₁ -C₂ -alkyl, benzyl, trimethylsilylmethyl or foran ammonium equivalent, a C₁ -C₃ -alkylammonium equivalent, a sodiumequivalent, or a potassium equivalent, or for the group ##STR10##wherein R⁷ stands for hydrogen, methyl, phenyl, furyl, thienyl orpyridyl,

R⁸ stands for methoxy or ethoxy,

R⁹ stands for methoxy or ethoxy and

Q stands for oxygen or sulphur or

R⁶ stands for the (--CH₂ --)_(n--R) ¹⁰ group,

wherein

n stands for the numbers 0, 1 or 2 and

R¹⁰ stands for a heterocyclic radical from the series comprising furyl,tetrahydrofuryl, thienyl, perhydropyranyl, oxazolyl, thiazolyl anddioxolanyl, each of which is optionally substituted by chlorine and/ormethyl.

The R isomers of the particularly preferred compounds of the formula (I)are very particularly preferred.

If, for example, 5-(4-trifluoromethyl-phenoxy)-1-naphthol and ethylα-bromo-propionate are used as starting materials for process (a)according to the invention then the course of the reaction can berepresented by the following equation: ##STR11##

If, for example, 3,4,5-trichloro-benzotrifluoride aud propylα-(5-hydroxy-naphthalen-1-yl-oxy)-propionate are used as startingmaterials for process (b) according to the iuvention then the course ofthe reaction can be represented by the following equation: ##STR12##

If, for example, methylα-(5-(2-chloro-4-trifluoromethyl-phenoxy)-naphthalen-1-yl-oxy)-propionateand sodium hydroxide solution are used as starting materials for process(c) according to the invention then the course of the reaction can berepresented by the following equation: ##STR13##

If, for example,α-(5-(2,6-dichloro-3-fluoro-4-trifluoromethyl-phenoxy)-naphthalen-1-yl-oxy)-propionicacid and thionyl chloride are used as starting materials for process (d)according to the invention then the course of the reaction can berepresented by the following equation: ##STR14##

If, for example,α-(5-(2-chloro-6-fluoro-4-trifluoromethyl-phenoxy)-naphthalen-1-yl-oxy)-propionylchloride and butanol are used as starting materials for process (e)according to the invention then the course of the reaction can berepresented by the following equation: ##STR15##

If, for example,α-(5-(2,3,6-trichloro-4-trifluoromethyl-phenoxy)-naphthalen-1-yl-oxy)-propionicacid and trimethylsilylmethyl chloride are used as starting materialsfor process (f) according to the invention then the course of thereaction can be represented by the following equation: ##STR16##

Formula (II) provides a general definition of the 5-aryloxy-1-naphtholsto be used as starting materials for the preparation of compounds of theformula (I) in process (a) according to the invention.

In formula (II), R¹, R², R³, R⁴ and R⁵ preferably or in particular havethose meanings which have already been given above as preferable orparticularly preferable for R¹, R², R³, R⁴ and R⁵ in connection with thedescription of the compounds of the formula (I) according to theinvention.

Examples of the starting materials of the formula (II) which may bementioned are: 5-(4-trifluoromethyl-phenoxy)-1-naphthol,5-(2-chloro-4-trifluoromethyl-phenoxy)-1-naphthol,5-(2,6-dichloro-4-trifluoromethyl-phenoxy)-1-naphthol,5-(2-chloro-6-fluoro-4-trifluoromethyl-phenoxy-1-naphthol,5-(2,6-dichloro-3-fluoro-4-trifluoromethyl-phenoxy)-1-naphthol and5-(2,3,6-trichloro-4-trifluoromethyl-phenoxy)-1-naphthol.

The starting materials of the formula (II) were hitherto unknown fromthe literature. The compounds of the formula (II) are obtained whencorresponding halogeno-benzene derivatives of the general formula (IV)##STR17## in which R¹, R², R³, R⁴, R⁵ and X have the abovementionedmeanings,

are reacted with 1,5-dihydroxynaphthalene in the presence of an acidacceptor, such as, for example, sodium hydroxide or potassium hydroxide,and in the presence of a diluent, such as, for example,dimethylformamide, dimethylacetamide, dimethyl sulphoxide,tetramethylenesulphone or N-methyl-pyrrolidone, at temperatures between20° C. and 150° C., and are worked up by customary methods.

Formula (IV) provides a general definition of the halogeno-benzenederivatives. In formula (IV), R¹, R², R³, R⁴ and R⁵ preferably or inparticular have those meanings which have already been given aspreferable or as particularly preferable for R¹, R², R³, R⁴ and R⁵ inconnection with the description of the compounds of the formula (I)according to the invention, and X preferably stands for chlorine orfluorine.

Examples of the halogeno-benzene derivatives of the formula (IV) whichmay be mentioned are: 3-cyano-4-chloro-benzotrifluoride,4-chloro-benzotrifluoride, 3,4-dichloro-benzotrifluoride,3,4,5-trichloro-benzotrifluoride,3,4-dichloro-5-fluoro-benzotrifluoride,2,3,4,5-tetrachloro-benzotrifluoride,3,5-dichloro-2,4-difluorobenzotrifluoride and3-chloro-4,5-difluoro-benzotrifluoride.

The compounds of the formula (IV) are known and/or can be prepared byprocesses which are known per se (compare J. Chem. Soc. 1969, 211-217;ibid. 1971, 1547-1549; EP-A 34,402; U.S. Pat. No. 4,424,396; EP-A145,314; FR-A 2,538,380 (Chem. Abstracts 102 (1985), 61914x)).

Formula (III) provides a general definition of the propionic acidderivatives additionally to be used as starting materials in process (a)according to the invention. In formula (III), Z preferably or inparticular has that meaning which has already been given above aspreferable or particularly preferable in connection with the descriptionof the compounds of the formula (I) according to the invention, and Ypreferably stands for chlorine, bromine, iodine, C₁ -C₄-alkylsulphonyloxy which is optionally substituted by fluorine orchlorine, or phenylsulphonyloxy which is optionally substituted byfluorine, chlorine, bromine or methyl, in particular for chlorine,bromine, methylsulphonyloxy, phenylsulphonyloxy or4-methyl-phenylsulphonyloxy.

Examples of the compounds of the formula (III) which may be mentionedare: methyl, ethyl, propyl, isopropyl, butyl, isobutyl and sec-butylα-chloro-, α-bromo- and α-iodo-propionates, and methyl, ethyl, propyl,butyl, isopropyl, isobutyl and sec-butyl α-methylsulphonyloxy-,α-ethylsulphonyloxy-, α-propylsulphonyloxy-, α-butylsulphonyloxy-,α-trifluoromethylsulphonyloxy-, α-phenylsulphonyloxy- andα-(4-methyl-phenylsulphonyloxy)-propionates.

The mentioned compounds of the formula (III) in each case the R isomers,the S isomers and the racemic mixtures of these isomers are taken tomean.

The starting materials of the formula (III) are known and/or can beprepared by processes which are known per se (compare DE-OS (GermanPublished Specification) 2,758,002, DE-OS (German PublishedSpecification) 2,854,542).

Process (a) according to the invention for the preparation of the newcompounds of the formula (I) is preferably carried out using diluents.Suitable diluents in this case are practically all inert organicsolvents. These preferably include aliphatic and aromatic, optionallyhalogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane,petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylenechloride, ethylene chloride, chloroform, carbon tetrachloride,chlorobenzene and o-dichlorobenzene, ethers such as diethyl ether anddibutyl ether, glycol dimethyl ether and diglycol dimethyl ether,tetrahydrofuran and dioxane, ketones such as acetone, methyl ethylketone, methyl isopropyl ketone and methyl isobutyl ketone, esters suchas methyl acetate and ethyl acetate, nitriles such as, for example,acetonitrile and propionitrile, amides such as, for example,dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone and alsodimethyl sulphoxide, tetramethylenesulphone and hexamethylphosphorictriamide.

Acid acceptors which can be employed in process (a) according to theinvention are all acid-binding agents conventionally utilizable forreactions of this type. Alkali metal hydroxides such as, for example,sodium hydroxide and potassium hydroxide, alkaline earth metalhydroxides such as, for example, calcium hydroxide, alkali metalcarbonates and alkali metal alcoholates such as sodium carbonate andpotassium carbonate, and sodium tert-butylate and potassiumtert-butylate, and furthermore aliphatic, aromatic or heterocyclicamines, for example triethylamine, trimethylamine, dimethylaniline,dimethylbenzylamine, pyridine, 1,5-diazabicyclo-[4,3,0]-non-5-ene (DBN),1,8-diazabicyclo-[5,4,0]-undec-7-ene (DBU) and1,4-diazabicyclo-[2,2,2]-octane (DABCO) are preferable.

The reaction temperatures can be varied within a relatively wide rangewhen carrying out process (a) according to the invention. In general,the process is carried out at temperatures between 0° C. and 150° C.,preferably at temperatures between 20° C. and 100° C.

Process (a) according to the invention is generally carried out atatmospheric pressure. However, it is also possible to work at elevatedor reduced pressure.

For carrying out process (a) according to the invention, between 0.5 and1.2 moles, preferably between 0.7 and 1.0 mole, of propionic acidderivative of the formula (III) are generally employed per mole of5-aryloxy-1-naphthol of the formula (II). The reaction components aregenerally combined at room temperature or with slight cooling and arethen stirred--if desired at elevated temperature--until completion ofthe reaction.

Working up can be carried out in a customary manner. For example, thereaction mixture is stirred or shaken with an acid, such as, forexample, hydrochloric acid or sulphuric acid and water, and also anorganic solvent which is practically immiscible with water, such as, forexample, methylene chloride or toluene, and the organic phase isseparated off, washed with water, dried and filtered. The product of theformula (I) remaining in the residue after concentration of the filtratecan be purified in a customary manner, for example by columnchromatography.

The halogeno-benzene derivatives of the formula (IV) to be used asstarting materials in process (b) according to the invention havealready been described above.

Formula (V) provides a general definition of theα-(5-hydroxy-naphthalen-1-yl-oxy)-propionic acid derivatives to be usedfurthermore as starting materials in process (b) according to theinvention. In formula (V), Z preferably or in particular has thatmeaning which has already been given above as preferable or particularlypreferable in connection with the description of the compounds of theformula (I) according to the invention.

Examples of the starting materials of the formula (V) which may bementioned are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl andsec-butyl α-(5-hydroxy-naphthalen-1-yl-oxy)-propionates.

The starting materials of the formula (V) are known and/or can beprepared by processes which are known per se (compare JP 79/32477, citedin Chem. Abstracts 91 (1979), 91510j).

Process (b) is preferably carried out using a diluent. Possible diluentsare above all those which have already been mentioned in the descriptionof process (a) according to the invention. Aprotic polar organicsolvents, such as, for example, acetone, acetonitrile, methyl ethylketone, propionitrile, dimethylformamide, dimethylacetamide, dimethylsulphoxide, sulpholane and N-methylpyrrolidone are particularlypreferred.

Process (b) is preferably carried out in the presence of an acidacceptor. Possible acid acceptors are above all those which have alreadybeen mentioned in the description of process (a) according to theinvention.

The reaction temperatures can be varied within a relatively wide rangewhen carrying out process (b) according to the invention. In general,the process is carried out at temperatures between 0° C. and 200° C.,preferably at temperatures between 20° C. and 150° C.

Process (b) according to the invention is generally carried out atatmospheric pressure. However, it is also possible to work at elevatedor reduced pressure.

For carrying out process (b) according to the invention, between 0.5 and2 moles, preferably between 0.7 and 1.5 moles, ofα-(5-hydroxy-naphthalen-1-yl-oxy)-propionic acid derivative of theformula (V) are generally employed per mole of halogeno-benzenederivative of the formula (IV).

Reaction and working up can be carried out as described above forprocess (a).

Formula (I) provides a general definition of the compounds to be used asstarting materials for carrying out process (c) according to theinvention, with the proviso that Z stands for methoxy or ethoxy. In thiscase, the radicals R¹, R², R³, R⁴ and R⁵ preferably or in particularhave those meanings which have already been given above as preferable orparticularly preferable in the context of the description of thecompounds of the formula (I) according to the invention.

Examples of the starting materials for process (c) which may bementioned are: methyl and ethyl α-(5-(4-trifluoromethyl)-phenoxy)-,α-(5-(2-chloro-4-trifluoromethyl-phenoxy)-,α-(5-(2,6-dichloro-4-trifluoromethyl-phenoxy)-,α-(5-(2-chloro-6-fluoro-4-trifluoromethyl-phenoxy)-,α-(5-(2,3,6-trichloro-4-trifluoromethyl-phenoxy)- andα-(5-(2,6-dichloro-3-fluoro-4-trifluoromethyl-phenoxy)-naphthalen-1-yl-oxy)-propionates.

The starting materials of the formula (I) described above for process(c) are new compounds according to the invention; they can be preparedby process (a) or (b) according to the invention.

Process (c) is carried out using alkali metal hydroxides. Examples ofthese which may be mentioned are lithium hydroxide, sodium hydroxide andpotassium hydroxide. Sodium hydroxide is preferably used.

Process (c) is carried out in the presence of water and if appropriatein the presence of an organic solvent. Alcohols, such as, for example,methanol or ethanol are preferably employed as organic solvents.

The customary mineral acids, such as, for example, hydrochloric acid orsulphuric acid are used in process (c) for acidification.

The reaction temperatures can be varied within a relatively wide rangewhen carrying out process (c) according to the invention. In general,the process is carried out at temperatures between 10° C. and 150° C.,preferably at temperatures between 20° C. and 100° C.

Process (c) according to the invention is generally carried out atatmospheric pressure However, it is also possible to work at elevated orreduced pressure.

For carrying out process (c), between 0.1 and 10 moles, preferablybetween 0.5 and 2 moles, of alkali metal hydroxide are generallyemployed per mole of starting compound of the formula (I). The reactioncomponents are generally combined at room temperature and the reactionmixture is stirred, at elevated temperature if desired, until the end ofthe reaction. The resulting crystalline reaction product can beisolated--if appropriate after concentration, cooling andacidification--by filtering with suction.

Formula (I) provides a general definition of the compounds to be used asstarting materials in process (d) according to the invention, with theproviso that Z stands for hydroxyl. In this case, the radicals R¹, R²,R³, R⁴ and R⁵ preferably or in particular have those meanings which havealready been given as preferable or particularly preferable in thecontext of the description of the compounds of the formula (I) accordingto the invention.

Examples of the starting materials for process (d) which may bementioned are: α-(5-(4-trifluoromethyl-phenoxy)-,α-(5-(2-chloro-4-trifluoromethyl-phenoxy)-,α-(5-(2,6-dichloro-4-trifluoromethylphenoxy)-,α-(5-(2-chloro-6-fluoro-4-trifluoromethyl-phenoxy)-,α-(5-(2,3,6-trichloro-4-trifluoromethyl-phenoxy)- andα-(5-(2,6-dichloro-3-fluoro-4-trifluoromethyl-phenoxy)-naphthalen-1-yl-oxy)-propionicacid.

The starting materials of the formula (I) described above for process(d) are new compounds according to the invention; they can be preparedby process (c) according to the invention.

Process (d) is carried out using a halogenating agent. The customaryagents for the conversion of carboxylic acids to carboxyl halides can beemployed. Examples of these which may be mentioned are phosgene, thionylchloride, phosphoryl chloride and benzotrichloride. Thionyl chloride ispreferably used as the halogenating agent.

Process (d) is carried out in the presence of a catalyst if desired. Thecustomary catalysts for the preparation of acid chlorides from acids,such as, for example, pyridine or dimethylformamide, can be used.

Process (d) is carried out in the presence of a diluent if desired.Inert organic solvents are from the series comprising the halogenatedhydrocarbons are preferable, such as, for example, methylene chloride,chloroform, tetrachloromethane or 1,2-dichloroethane.

The reaction temperatures can be varied within a relatively wide rangewhen carrying out process (d) according to the invention. In general,the process is carried out at temperatures between 0° C. and 100° C.,preferably at temperatures between 10° C. and 90° C.

Process (d) is generally carried out at atmospheric pressure.

For carrying out process (d), between 1 and 100 moles, preferablybetween 2 and 50 moles, of halogenating agent are generally employed permole of starting compound of the formula (I). The reaction componentsare generally combined at room temperature and the reaction mixture isstirred, if desired at elevated temperature until the end of thereaction. The reaction product remaining after removing the volatilecomponents by distillation under reduced pressure can be purified byrecrystallization, but can also be employed without further purificationfor further reactions.

Formula (I) provides a general definition of the compounds to be used asstarting materials for process (e) according to the invention, with theproviso that Z stands for halogen. In this case, the radicals R¹, R²,R³, R⁴ and R⁵ preferably or in particular have those meanings which havealready been given above as preferable or particularly preferable in thecontext of the description of the compounds of the formula (I) accordingto the invention and Z preferably stands for fluorine, chlorine orbromine, in particular for chlorine.

Examples of the starting materials for process (e) which may bementioned are: α-(5-(4-trifluoromethyl-phenoxy)-,α-(5-(2-chloro-4-trifluoromethyl-phenoxy)-,α-(5-(2,6-dichloro-4-trifluoromethylphenoxy)-,α-(5-(2-chloro-6-fluoro-4-trifluoromethyl-phenoxy)-,α-(5-(2,3,6-trichloro-4-trifluoromethyl-phenoxy)- andα-(5-(2,6-dichloro-3-fluoro-4-trifluoromethyl-phenoxy)-naphthalen-1-yl-oxy)-propionylchloride.

The starting materials of the formula (I) described above for process(e) are new compounds according to the invention; they can be preparedby process (d) according to the invention.

Formula (VI) provides a general definition of the compounds furthermoreto be employed as starting materials in process (e) according to theinvention. In formula (VI), Z preferably or in particular has thatmeaning which has already been given above as preferable or particularlypreferable in connection with the description of the compounds of theformula (I) according to the invention.

Examples of the starting materials of the formula (VI) which may bementioned are: methylamine, ethylamine, propylamine, isopropylamine,aniline, cyanamide, dimethylamine, diethylamine, hydroxylamine,o-methylhydroxylamine, hydrazine, methylsulphonylhydrazine, methanol,ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol,2-methoxy-ethanol, 2-ethoxy-ethanol, 2-methylthio-ethanol,2-ethylthio-ethanol, 2-benzyloxy-ethanol, 3-benzyloxy-propanol,2-benzylthio-ethanol, diethyl and dimethyl hydroxymethanephosphonate,dimethyl and diethyl 1-hydroxy-ethane-phosphonate, dimethyl and diethyl1-hydroxy-1-phenyl-methanephosphonate, acetone oxime, 3-hydroxyfuran,furfuryl alcohol, perhydrofurfuryl alcohol, methyl and ethyl lactate andmethyl and ethyl glycolate.

These compounds are known synthesis chemicals.

Process (e) is preferably carried out using a diluent. Possible diluentsare above all those which have already been mentioned in the descriptionof process (a) according to the invention.

Process (e) is preferably carried out in the presence of an acidacceptor. Possible acid acceptors are above all those which have alreadybeen mentioned in the description of process (a) according to theinvention.

The reaction temperatures can be varied within a relatively wide rangewhen carrying out process (e) according to the invention. In general,the process is carried out at temperatures between -20° C. and +100° C.,preferably at temperatures between 0° C. and 50° C.

Process (e) according to the invention is generally carried out atatmospheric pressure. However, it is also possible to work at elevatedor reduced pressure.

For carrying out process (e) according to the invention, the startingmaterials required in each case are generally employed in approximatelyequimolar amounts. However, it is also possible to use one of the twocomponents employed in each case in a relatively large excess. Thereactions are generally carried out in a suitable diluent in thepresence of an acid acceptor and the reaction mixture is stirred forseveral hours at the temperature necessary in each case.

In process (e) according to the invention working up in each case takesplace according to customary methods. For example, the reaction mixtureis diluted--if desired after concentration--with water and the desiredreaction product is extracted with an organic solvent which ispractically immiscible with water, for example methylene chloride,chloroform, diethyl ether, toluene or xylene. The organic extractionsolution is washed with water, dried using a customary drying agent,such as, for example, sodium sulphate, and filtered. After concentratingthe filtrate, the compounds of the formula (I) are obtained as crudeproducts which can be purified in a customary manner, for examplechromatographically and/or by recrystallization.

Formula (I) provides a general definition of the compounds to be used asstarting materials in process (f) according to the invention, with theproviso that Z stands for hydroxyl. In this case, the radicals R¹, R²,R³, R⁴ and R⁵ preferably or in particular have those meanings which havealready been given above as preferable or particularly preferable in thecontext of the description of the compounds of the formula (I) accordingto the invention.

Examples of the starting materials of the formula (I) for process (f)which may be mentioned are: α-(5-(4-trifluoromethyl-phenoxy)-,α-(5-(2-chloro-4-trifluoromethyl-phenoxy)-,α-(5-(2,6-dichloro-4-trifluoromethylphenoxy)-,α-(5-(2-chloro-6-fluoro-4-trifluoromethyl-phenoxy)-,α-(5-(2,3,6-trichloro-4-trifluoromethyl-phenoxy)- andα-(5-(2,6-dichloro-3-fluoro-4-trifluoromethyl-phenoxy)-naphthalen-1-yl-oxy)-propionicacid.

The starting materials of the formula (I) described above for process(f) are new compounds according to the invention; they can be preparedby process (c) according to the invention.

Formula (VII) provides a general definition of the compounds furthermoreto be employed as starting materials in process (f) according to theinvention. In formula (VII), R⁶ preferably stands for C₁ -C₆ -alkyl, C₃-C₄ -alkenyl, C₃ -C₄ -alkinyl, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, C₁ -C₄-alkylthio-C₁ -C₄ -alkyl, phenoxy-C₁ -C₃ -alkyl, trimethylsilylmethyl,phenylthio-C₁ -C₃ -alkyl, benzyloxy-C₁ -C₃ -alkyl, benzylthio-C₁ -C₃-alkyl or C₁ -C₄ -alkoxy-carbonyl-C₁ -C₂ -alkyl, and X¹ stands forchlorine, bromine or iodine.

In particular, R⁶ in formula (VII) stands for trimethylsilylmethyl andX¹ stands for chlorine.

Trimethylsilylmethyl chloride is particularly preferred as the startingcompound of the formula (VII) for process (f).

The starting materials of the formula (VII) are known synthesischemicals.

Process (f) is preferably carried out using a diluent. Possible diluentsare above all those which have already been mentioned in the descriptionof process (a) according to the invention. Acetone, acetonitrile anddimethylformamide are particularly preferred.

Process (f) is preferably carried out in the presence of an acidacceptor. Possible acid acceptors are above all those which have alreadybeen mentioned in the description of process (a) according to theinvention. 1,8-Diazabicyclo-[5,4,0]-undec-7-ene (DBU) is particularlypreferred.

The reaction temperatures can be varied within a relatively wide rangewhen carrying out process (f) according to the invention. In general,the process is carried out at temperatures between 0° C. and 150° C.,preferably at temperatures between 20° C. and 100° C.

Process (f) according to the invention is generally carried out atatmospheric pressure. However, it is also possible to work at elevatedor reduced pressure.

For carrying out process (f), between 1 and 3 moles, preferably between1.1 and 2.5 moles, of starting compound of the formula (VII) aregenerally employed per mole of starting compound of the formula (I).

Reaction and working up can be carried out as described above forprocess (a).

The active compounds according to the invention can be used asdefoliants, desiccants, agents for destroying broad-leaved plants and,especially, as weedkillers. By weeds, in the broadest sense, there areto be understood all plants which grow in locations where they areundesired. Whether the substances according to the invention act astotal or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio,Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala,Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis,Papaver and Centaurea.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum,Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus andAllium.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

The compounds are suitable, depending on the concentration, for thetotal combating of weeds, for example on industrial terrain and railtracks, and on paths and squares with or without tree plantings.Equally, the compounds can be employed for combating weeds in perennialcultures, for example afforestations, decorative tree plantings,orchards, vineyards, citrus groves, nut orchards, banana plantations,coffee plantations, tea plantations, rubber plantations, oil palmplantations, cocoa plantations, soft fruit plantings and hopfields, andfor the selective combating of weeds in annual cultures.

The active compounds according to the invention are particularlysuitable for the selective combating of monocotyledon weeds inmonocotyledon and dicotyledon cultures, above all by the post-emergencemethod.

The active compounds can be converted to the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusting agents, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and very fine capsules in polymeric substances.

These formulations are produced in known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surface-active agents, thatis emulsifying agents and/or dispersing agents and/or foam-formingagents.

In the case of the use of water as an extender, organic solvents can,for example, also be used as auxiliary solvents. As liquid solvents,there are suitable in the main: aromatics, such as xylene, toluene oralkyl naphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample petroleum fractions, mineral and vegetable oils, alcohols, suchas butanol or glycol as well as their ethers and esters, ketones, suchas acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water.

As solid carriers there are suitable: for example ammonium salts andground natural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly disperse silicic acid, alumina and silicates,as solid carriers for granules there are suitable: for example crushedand fractionated natural minerals such as calcite, marble, pumice,sepiolite and dolomite, as well as synthetic granules of inorganic andorganic meals, and granules of organic material such as sawdust, coconutshells, corn cobs and tobacco stalks; as emulsifying and/or foam-formingagents there are suitable: for example non-ionic and anionicemulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylenefatty alcohol ethers, for example alkylaryl polyglycol ethers,alkylsulphonates, alkyl sulphates, arylsulphonates as well as albuminhydrolysis products; as dispersing agents there are suitable: forexample lignin sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Further additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

For combating weeds, the active compounds according to the invention canbe used as such or in the form of their formulations or alternatively asmixtures with known herbicides, finished formulations or tank mixesbeing possible.

Suitable components for the mixtures are known herbicides such as, forexample,1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dione(AMETHYDIONE) or N-(2-benzthiazolyl)-N,N'-dimethyl-urea(METABENZTHIAZURON) for combating weeds in cereals;4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (METAMITRON) forcombating weeds in sugar beets and4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one(METRIBUZIN) for combating weeds in soy beans, and furthermore also2,4-dichlorophenoxyacetic acid (2,4-D); 4-(2,4-dichlorophenoxy)-butyricacid (2,4-DB); 2,4-dichlorophenoxypropionic acid (2,4-DP);5-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitrobenzoic acid(ACIFLUORFEN); methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate (BIFENOX);3,5-dibromo-4-hydroxy-benzonitrile (BROMOXYNIL); ethyl2-{[(4-chloro-6-methoxy-2-pyrimidinyl)-aminocarbonyl]-aminosulphonyl}-benzoate(CHLORIMURON);2-chloro-N-{[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]carbonyl}-benzenesulphonamide(CHLORSULFURON); N,N-dimethyl-N'-(3-chloro-4-methylphenyl)-urea(CHLORTOLURON); N,N-dimethyl-N'-3-trifluoromethylphenyl)-urea(FLUOMETURON);5-(2-chloro-4-trifluoromethyl-phenoxy)-N-methylsulphonyl-2-nitrobenzamide(FOMESAFEN); methyl 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-4(5)-methylbenzoate(IMAZAMETHABENZ);2-[5-methyl-5-(1-methylethyl)-4-oxo-2-imidazolin-2-yl]-3-quinolinecarboxylicacid (IMAZAQUIN);2-[4,5-dihydro-4-methyl-4-isopropyl-5-oxo-(1H)-imidazol-2-yl]-5-ethyl-pyridine-3-carboxylicacid (IMAZETHAPYR); 3,5-diiodo-4-hydroxybenzonitrile (IOXYNIL);N,N-dimethyl-N'-(4-isopropylphenyl)-urea (ISOPROTURON);(2-ethoxy-1-methyl-2-oxo-ethyl)5-[2-chloro-4-(trifluoromethyl)-phenoxy]-2-nitrobenzoate (LACTOFEN);(2-methyl-4-chlorophenoxy)-acetic acid (MCPA);(4-chloro-2-methylphenoxy)-propionic acid (MCPP);N-methyl-2-(1,3-benzthiazol-2-yloxy)-acetanilide (MEFENACET);2-{[[((4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)-carbonyl]-amino]-sulphonyl}-benzoicacid or its methyl ester (METSULFURON);(2-chloro-4-trifluoromethylphenyl)( 3-ethoxy-4-nitro-phenyl) ether(OXYFLUORFEN); N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitroaniline(PENDIMETHALIN); methyl3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl]-amino]-sulphonyl]-thiophene-2-carboxylate(THIAMETURON); 3,5,6-trichloro-2-pyridyloxyacetic acid (TRICLOPYR) and2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline (TRIFLURALIN), andalso 4-amino-6-tert.-butyl-3-ethylthio-1,2,4-triazin-5-(4H)-one(ETHIOZIN), 3-isopropyl-2,1,3-benzothiadiazin-4-one-2,2-dioxide(BENTAZON), N-phosphonomethylglycine (GLYPHOSPHATE) andO-(6-chloro-3-phenyl-pyridazin-4-yl) S-octyl thiocarbonate (PYRIDATE).Surprisingly, some mixtures also show a synergistic action.

Mixtures with other known active compounds, such as fungicides,insecticides, acaricides, nematicides, bird repellents plant nutrientsand agents which improve soil structure, are also possible.

The active compounds can be used as such, in the form of theirformulations or in the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, emulsions, powders, pastesand granules. They are used in the customary manner, for example bywatering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied eitherbefore or after emergence of the plants.

They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a substantial range.It depends essentially on the nature of the desired effect. In general,the amounts used are between 0.01 and 10 kg of active compound perhectare of soil surface, preferably between 0.05 and 5 kg per ha.

The preparation and use of the active compounds according to theinvention can be seen from the following examples.

PREPARATION EXAMPLES Example 1 ##STR18##

A mixture of 11.6 g (0.03 mol) of5-(2-chloro-4-trifluoromethyl-phenoxy)-1-naphthol, 5.4 g (0.02 mol) ofethyl (S)-α-(4-methyl-phenylsulphonyloxy)-propionate, 4.2 g of potassiumcarbonate and 100 ml of acetonitrile is heated to boiling under refluxfor 15 hours. After cooling to 20° C., the reaction mixture is acidifiedwith 2N hydrochloric acid and shaken with toluene. The organic phase isseparated off, washed with water, dried using sodium sulphate andfiltered. The solvent is carefully removed from the filtrate bydistillation in a water-jet vacuum. The residue is purified by columnchromatography (toluene/hexane on silica gel).

1.6 g (18% of theory) of ethyl(R)-α-(5-(2-chloro-4-trifluoromethyl-phenoxy)-naphthalen-1-yl-oxy)-propionateare obtained as an oily residue of refractive index n_(d) ²⁰ =1.5611.

The compounds of the formula (I) ##STR19## shown in Table 1 below can beobtained analogously to Example 1 and in accordance with the generaldescription of the preparation process according to the invention.

                                      TABLE 1                                     __________________________________________________________________________    Examples of the compounds of the formula (I)                                  Example                                                                       No.  R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                          R.sup.4                                                                          R.sup.5                                                                          Z             Physical data                               __________________________________________________________________________     2   H  H  CF.sub.3                                                                         H  H  OC.sub.2 H.sub.5                                                                            n.sub.D.sup.20 = 1.5728                      3   Cl H  CF.sub.3                                                                         H  Cl OC.sub.2 H.sub.5                                                                            amorphous                                    4   Cl H  CF.sub.3                                                                         H  F  OCH.sub.3                                                  5   Cl Cl CF.sub.3                                                                         H  Cl OC.sub.3 H.sub.7                                           6   Cl F  CF.sub.3                                                                         H  Cl OC.sub.4 H.sub.9                                           7   H  H  CF.sub.3                                                                         H  H  OH                                                         8   Cl H  CF.sub.3                                                                         H  H  OH                                                         9   Cl H  CF.sub.3                                                                         H  F  OH                                                        10   Cl Cl CF.sub.3                                                                         H  Cl OH                                                        11   Cl F  CF.sub.3                                                                         H  Cl OH                                                        12   Cl H  CF.sub.3                                                                         H  H  Cl                                                        13   Cl H  CF.sub.3                                                                         H  Cl OH                                                        14   Cl H  CF.sub.3                                                                         H  Cl Cl                                                        15   Cl Cl CF.sub.3                                                                         H  Cl Cl                                                        16   Cl H  CF.sub.3                                                                         H  Cl OCH(CH.sub.3).sub.2                                       17   Cl H  CF.sub.3                                                                         H  H  OC.sub. 4 H.sub.9                                         18   Cl H  CF.sub.3                                                                         H  Cl OCH.sub.2 COOCH.sub.3                                     19   Cl H  CF.sub.3                                                                         H  H  OCH.sub.2 COOC.sub.4 H.sub.9                              20   Cl H  CF.sub.3                                                                         H  F                                                                                 ##STR20##                                                21   Cl H  CF.sub.3                                                                         H  Cl SCH.sub.2 COOCH.sub.3                                     22   Cl Cl CF.sub.3                                                                         H  Cl OCH.sub.2 CH.sub.2 OCH.sub.3                              23   Cl H  CF.sub.3                                                                         H  Cl OCH.sub.2 CH.sub.2 SC.sub.2 H.sub.5                       24   Cl H  CF.sub.3                                                                         H  H                                                                                 ##STR21##                                                25   Cl H  CF.sub.3                                                                         H  H                                                                                 ##STR22##                                                26   Cl Cl CF.sub.3                                                                         H  Cl SC.sub.2 H.sub.5                                          27   Cl H  CF.sub.3                                                                         H  Cl NHCH(CH.sub.3).sub.2                                      28   Cl H  CF.sub.3                                                                         H  H  N(C.sub.2 H.sub.5).sub.2                                  29   Cl H  CF.sub.3                                                                         H  Cl                                                                                ##STR23##                                                30   Cl H  CF.sub.3                                                                         H  H                                                                                 ##STR24##                                                31   Cl H  CF.sub.3                                                                         H  H  NHOCH.sub.3                                               32   Cl H  CF.sub.3                                                                         H  H  NHOC.sub.2 H.sub.5                                        33   Cl H  CF.sub.3                                                                         H  Cl NHCH.sub.2 COOC.sub.2 H.sub.5                             34   Cl H  CF.sub.3                                                                         H  H  NHNHSO.sub.2 CH.sub.3                                     35   Cl H  CF.sub.3                                                                         H  Cl OCH.sub.2 Si(CH.sub.3).sub.3                              36   CN H  CF.sub.3                                                                         H  H  OC.sub.2 H.sub.5                                                                            (amorphous)                                 37   Cl H  CF.sub.3                                                                         H  Cl                                                                                ##STR25##                                                __________________________________________________________________________

STARTING MATERIALS OF THE FORMULA (II) Example (II-1) ##STR26##

20.4 g (0.095 mol) of 3,4-dichloro-benzotrifluoride are slowly addedwith stirring to a mixture of 28.4 g (0.18 mol) of1,5-dihydroxy-naphthalene, 10.1 g (0.18 mol) of potassium hydroxidepowder and 100 ml of dimethyl sulphoxide, which is heated at 120° C.,and the reaction mixture is stirred at 120° C. for 10 hours. Aftercooling to 20° C., the mixture is acidified using 2N hydrochloric acidand stirred with toleune. The crystalline product resulting,1,5-dihydroxynaphthalene, is isolated by filtering with suction anddiscarded. The toluene phase is separated off and dried using sodiumsulphate. After filtration, the solvent is carefully removed bydistillation in vacuo.

11.6 g (36% of theoryl) of5-(2-chloro-4-trifluoromethyl-phenoxyl)-1-naphthol are obtained as anamorphous residue

(¹ H-NMR (CDCl₃), δ (R²): 7.73 ppm, when R¹ =Cl, R³ =CF₃).

The starting materials of the formula (II) shown in Table 2 below can beprepared analogously to Example (II-1). ##STR27##

                  TABLE 2                                                         ______________________________________                                        Examples of the starting materials of the formula (II)                        Example                                                                       No.        R.sup.1  R.sup.2 R.sup.3                                                                              R.sup.4                                                                             R.sup.5                              ______________________________________                                        II-2       H        H       CF.sub.3                                                                             H     H                                    II-3       Cl       H       CF.sub.3                                                                             H     Cl                                   II-4       Cl       Cl      CF.sub.3                                                                             H     Cl                                   II-5       Cl       F       CF.sub.3                                                                             H     Cl                                   II-6       Cl       H       CF.sub.3                                                                             H     F                                    II-7       CN       H       CF.sub.3                                                                             H     H                                    ______________________________________                                    

USE EXAMPLES

The compound shown below is referred to as the comparison substance inthe following use examples: ##STR28## Ethylα-(7-(2-chloro-4-trifluoromethyl-phenoxy)-naphthalen-2-yl-oxy)-propionate(known from EP-A 179,015/Example 1).

Example A Post-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Test plants which have a height of 5-15 cm are sprayed with thepreparation of the active compound in such a way as to apply theparticular amounts of active compound desired per unit area. Theconcentration of the spray liquor is so chosen that the particularamounts of active compound desired are applied in 2,000 l of water/ha.After three weeks, the degree of damage to the plants is rated in %damage in comparison to the development of the untreated control. Thefigures denote:

0%=no action (like untreated control)

100%=total destruction

In this test the compound according to preparation Example (1), forexample, shows, together with good selectivity in soy beans, cotton andwheat, considerably stronger action against problem weeds, such as, forexample, Digitaria, Panicum and Setaria, than the comparison substance(A).

It will be appreciated that the instant specification and claims are setforth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:
 1. An α-(5-aryloxy-naphthalen-1-yl-oxy)-propionicacid derivative of the formula ##STR29## in which R¹ stands forhydrogen, halogen, cyano or trifluoromethyl,R² stands for hydrogen orhalogen, R³ stands for halogen, cyano, trifluoromethyl ortrifluoromethoxy, R⁴ stands for hydrogen or halogen, R⁵ stands forhydrogen or halogen and Z stands for halogen, hydroxyl, or for the--O--R⁶ group,wherein R⁶ stands for an optionally halogen-substitutedradical from the series comprising alkyl, alkenyl, alkinyl, alkoxyalkyl,or aralkyl.
 2. An α-5-(aryloxy-naphthalen-1-yl-oxy)-propionic acidderivative according to claim 1, in whichR¹ stands for hydrogen,fluorine, chlorine, bromine, cyano or trifluoromethyl, R² stands forhydrogen, fluorine or chlorine, R³ stands for fluorine, chlorine,bromine, cyano, trifluoromethyl or trifluoromethoxy, R⁴ stands forhydrogen, fluorine or chlorine, R⁵ stands for hydrogen, fluorine,chlorine or bromine and Z stands for chlorine, hydroxyl, group,whereinR⁶ stands for a radical from the group consisting of C₁ -C₆ -alkyl, C₃-C₄ -alkenyl, C₃ -C₄ -alkinyl, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, and benzyl.3. An α-(5-aryloxy-naphthalen-1-yl-oxy)-propionic acid derivativeaccording to claim 1, in whichR¹ stands for hydrogen, cyano, fluorine orchlorine, R² stands for hydrogen, fluorine or chlorine, R³ stands fortrifluoromethyl, R⁴ stands for hydrogen, fluorine or chlorine, R⁵ standsfor hydrogen, fluorine or chlorine and Z stands for chlorine, hydroxyl,or for the --O--R⁶ group,wherein R⁶ stands for C₁ -C₂ -alkyl-C₁ -C₂-alkoxy-C₁ -C₂ -alkyl, and benzyl.
 4. A substantially pure R enantiomerof a compound according to claim
 3. 5. A compound according to claim 1,wherein such compound is ethyl(R)-α-(5-(2-chloro-4-trifluoromethylphenoxy)-naphthalen-1-yl-oxy)-propionateof the formula ##STR30##
 6. A herbicidal composition comprising aherbicidally effective amount of a compound according to claim 1 and adiluent.
 7. A method of combating unwanted vegetation which comprisesapplying to such vegetation or to a locus from which it is desired toexclude such vegetation a herbicidally effective amount of a compoundaccording to claim
 1. 8. A method of combating unwanted vegetation whichcomprises applying to such vegetation or to a locus from which it isdesired to exclude such vegetation a herbicidally effective amount of acompound according to claim
 5. 9. A 5-aryloxy-1-naphthol of the formula##STR31## in which R¹ stands for hydrogen, halogen, cyano ortrifluoromethyl,R² stands for hydrogen, or halogen, R³ stands forhalogen, cyano, trifluoromethyl or trifluoromethoxy, R⁴ stands forhydrogen or halogen, and R⁵ stands for hydrogen or halogen.
 10. Acompound according to claim 1, wherein such compound is ethyl(5-(4-trifluoromethyl-phenoxy)-naphthalen-1-yl-oxy)-propionate of theformula ##STR32##
 11. A method of combating unwanted vegetation whichcomprises applying to such vegetation or to a locus from which it isdesired to exclude such vegetation a herbicidally effective amount of acompound according to claim 10.